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(11) | EP 2 588 539 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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CURABLE ORGANOPOLYSILOXANE COMPOSITION AND OPTICAL SEMICONDUCTOR DEVICE HÄRTBARE ORGANOPOLYSILOXANZUSAMMENSETZUNG UND OPTISCHES HALBLEITERBAUELEMENT COMPOSITION D'ORGANOPOLYSILOXANE DURCISSABLE ET DISPOSITIF OPTIQUE À SEMI-CONDUCTEUR |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
Technical Field
[0001] The present invention relates to a curable organopolysiloxane composition and to an optical semiconductor device having an optical semiconductor element that is sealed and/or bonded with a cured body of the aforementioned composition.
Background Art
[0003] Curable organopolysiloxane compositions are used for sealing and/or bonding optical semiconductor elements in optical semiconductor devices having optical semiconductor elements such as photocouplers, light-emitting diodes, solid-state image pickup elements, or the like. It is required that cured bodies of such compositions neither absorb nor scatter the light emitted or received from semiconductor elements. Furthermore, in order to improve reliability of the optical semiconductor devices, it is desired that the cured bodies could not discolor or decrease in the bonding strength.
[0004] Japanese Unexamined Patent Application Publication (hereinafter referred to as "Kokai") 2006-342200 discloses a curable organopolysiloxane composition that can form a cured body having high hardness and high light transmittance. However, the cured body produced from such a composition can be either easily damaged during manufacture or use of an optical semiconductor device, or can easily delaminate from the optical semiconductor element or a package of such element.
[0005] Furthermore, Kokai 2007-63538 and Kokai 2008-120843 disclose curable organopolysiloxane compositions that can form cured bodies having excellent impact-resistant properties. However, since with the lapse of time such cured bodies are subject to yellowing, they are not suitable for sealing or bonding optical semiconductor elements of optical semiconductor devices that are intended for long-time use at high temperatures.
[0007] It is an object of the present invention to provide a curable organopolysiloxane composition that can form a cured body having long-lasting properties of light transmittance and bondability, and having relatively low hardness. It is another object to provide an optical semiconductor device that possesses excellent reliability.
Disclosure of Invention
[0008] The curable organopolysiloxane composition of the invention comprises at least the following components:
- (A) an alkenyl-containing organopolysiloxane that comprises 40 to 70 wt.% of constituent
(A-1) and 30 to 60 wt.% of constituent (A-2), wherein
constituent (A-1) comprises an organopolysiloxane of the following average compositional formula:
(R13 SiO1/2)a (R12 SiO2/2)b (R1 SiO3/2)c (SiO4/2)d
where R1 designates phenyl groups, methyl groups, or alkenyl groups having 2 to 10 carbon atoms; 0.1 to 50 mole % of all R1 groups are alkenyl groups having 2 to 10 carbon atoms; methyl groups constitute 90 mole % or more of the sum of methyl and phenyl groups contained in R1; "a", "b", "c", and "d" are numbers that satisfy the following conditions: 0 ≤ a ≤ 0.05; 0.9 ≤ b ≤ 1; 0 ≤ c ≤ 0.03; 0 ≤ d ≤ 0.03; and a+b+c+d = 1;
constituent (A-2) comprises an organopolysiloxane of the following average compositional formula:
(R23 SiO1/2)e (R22 SiO2/2)f(R2 SiO3/2)g (SiO4/2)h (H1/2)i
where R2 designates phenyl groups, methyl groups, or alkenyl groups having 2 to 10 carbon atoms; 5 to 10 mole % of all R2 groups are alkenyl groups having 2 to 10 carbon atoms; methyl groups constitute 90 mole % or more of the sum of methyl and phenyl groups contained in R2; "e", "f', "g", "h" and "i" are numbers that satisfy the following conditions: 0.4 ≤ e ≤ 0.6; 0 ≤ f ≤ 0.05; 0 ≤ g ≤ 0.05; 0.4 ≤ h ≤ 0.6; 0.01 ≤ i ≤ 0.05; and e+f+g+h = 1; - (B) an organopolysiloxane that contains silicon-bonded hydrogen atoms and comprises
10 to 50 wt.% of constituent (B-1), 50 to 90 wt.% of constituent (B-2), and 0 to 30
wt.% of constituent (B-3), in an amount that the silicon-bonded hydrogen atoms in
component (B) are in the range of 0.5 to 2.0 moles per 1 mole of the total content
of alkenyl groups in component (A), wherein
constituent (B-1) comprises an organopolysiloxane that contains at least 0.5 wt.% of silicon-bonded hydrogen atoms and that is represented by the following average molecular formula:
R33 SiO (R32 SiO)j (R3H SiO)k SiR33
where R3 designates phenyl groups or methyl groups; methyl groups constitute 90 mole % or more of all groups contained in R3; "j" is a number in the range of 0 to 35; and "k" is a number in the range of 5 to 100;
constituent (B-2) comprises an organopolysiloxane that contains at least 0.5 wt.% of silicon-bonded hydrogen atoms and that is represented by the following average compositional formula:
(HR42 SiO1/2)l (R43 SiO1/2)m (R42 SiO2/2)n (R4 SiO3/2)o (SiO4/2)p (RSO1/2)q
where R4 designates phenyl groups or methyl groups; methyl groups constitute 90 mole % or more of all groups contained in R4; R5 designates hydrogen atoms or alkyl groups having 1 to 10 carbon atoms; and "1", "m", "n", "o", "p" and "q" are numbers that satisfy the following conditions: 0.4 ≤ 1 ≤ 0.7; 0 ≤ m ≤ 0.2; 0 ≤ n ≤ 0.05; 0 ≤ o ≤ 0.5; 0.3 ≤ p ≤ 0.6; 0 ≤ q ≤ 0.05; and l+m+n+o+p = 1;
constituent (B-3) is an organopolysiloxane represented by the following average molecular formula:
HR62 SiO (R62 SiO)r SiR62H
where R6 represents phenyl groups or methyl groups; methyl groups constitute at least 90% of all groups contained in R6; and "r" is a number in the range of 10 to 100; and - (C) a hydrosilylation-reaction catalyst, in an amount sufficient for curing the composition.
[0009] The composition of the invention may be further provided with (D) fumed silica having BET specific area of 20 to 200 m2/g and added in an amount of 1 to 10 parts by weight per 100 parts by weight of the sum of components (A) to (C).
[0010] When the composition of the invention is cured, it forms a cured body that has a type A durometer hardness in the range of 70 to 90 according to JIS K 6253 and that is suitable for use as an agent for sealing or bonding optical semiconductor elements, in particular light emitting diodes.
[0011] The optical semiconductor device of the present invention is characterized by having optical semiconductor elements sealed and/or bonded with the use of cured bodies of the aforementioned composition.
Effects of Invention
[0012] The curable organopolysiloxane composition of the present invention is characterized by forming a cured body having long-lasting properties of light transmittance and bondability, and having relatively low hardness. The optical semiconductor device of the invention is characterized by excellent reliability.
Brief Description of the Drawings
[0013] Fig. 1 is a sectional view of a surface-mount light emitting diode (LED) illustrated as an example of an optical semiconductor device of the invention.
Reference Numerals Used in the Description
[0014]
- 1
- housing made from polyphthalamide resin
- 2
- inner lead
- 3
- die pad
- 4
- bonding material
- 5
- LED chip
- 6
- bonding wire
- 7
- sealing material
Detailed Description of the Invention
[0015] Component (A), which is the main component of the composition of the invention, comprises an alkenyl-containing organopolysiloxane that consists of constituents (A-1) and (A-2) which are described below.
[0016] Constituent (A-1) is used for improving handleability of the composition and mechanical strength of a cured body. This constituent comprises an organopolysiloxane of the following average compositional formula:
(R13 SiO1/2)a (R12 SiO2/2)b (R1 SiO3/2)c (SiO4/2)d
where R1 designates phenyl groups, methyl groups, or alkenyl groups having 2 to 10 carbon atoms. The alkenyl groups of R1 can be represented by vinyl, allyl, butenyl, pentenyl, or hexenyl groups. Vinyl groups are preferable in view of their reactivity and ease of synthesis. However, 0.1 to 50 mole % of all R1 groups are alkenyl groups. This is because if the content of the alkenyl groups is below the recommended lower limit, a cured body of the composition will have low mechanical strength, and if, on the other hand, the content of the alkenyl group exceeds the recommended upper limit, a cured body will become brittle. Furthermore, when the sum of methyl groups and phenyl groups of R1 is assumed as 100%, the methyl groups should constitute 90 mole % of more. This is because if the content of methyl groups is below the recommended lower limit, a cured body of the composition can easily acquire a color at a high temperature. Furthermore, in the above formula, "a", "b", "c", and "d" are numbers that represent ratios of siloxane structural units, and that satisfy the following conditions: 0 ≤ a ≤ 0.05; 0.9 ≤ b ≤ 1; 0 ≤ c ≤ 0.03; 0 ≤ d ≤ 0.03; and a+b+c+d = 1. If the value of "a" exceeds the recommended upper limit, this will lead to significant decrease in viscosity of this constituent. This, in turn, will either impair handleability of the composition and make the present constituent volatile, or will decrease the weight of the composition during curing and reduce hardness of the cured body. If, on the other hand, the values of "c" and "d" exceed the recommended upper limit, this will increase viscosity of the present constituent, and will either impair handleability of the composition, or will make the cured body too brittle. The value of "b" is determined from the values of "a", "c", and "d". However, if the value of "b" is lower than the recommended lower limit, it will be impossible to impart either desired viscosity to the composition or a required hardness or mechanical strength to a cured body. Constituent (A-1) may have a linear, cyclic, partially cyclic, or a partially branched molecular structure. This constituent is liquid at 25°C. The viscosity of this constituent at 25°C should be in the range of 3 to 1,000,000 mPa·s, preferably 5 to 50,000 mPa·s. If the viscosity is below the recommended lower limit, this will reduce mechanical strength of a cured body, and, if, on the other hand, the viscosity exceeds the recommended upper limit, this will impair handleability of the composition.
[0017] Constituent (A-1) may be represented by organopolysiloxanes expressed by the average compositional formulas given below, where Vi stands for vinyl, Me stands for methyl, and Ph stands for phenyl.
(ViMe2 SiO1/2)0.01 (Me2 SiO2/2)0.988
(ViMe2 SiO1/2)0.007 (Me2 SiO2/2)0.993
(ViMe2) SiO1/2)0.004 (Me2 SiO2/2)0.996
(Me3 SiO1/2)0.007 (Me2 SiO2/2)0.983 (MeVi SiO2/2)0.010
(Me3 SiO1/2)0.01 (MeVi SiO1/2)0.01 (Me2 SiO2/2)0.96 (Me SiO3/2)0.02
(ViMe2 SiO1/2)0.005 (Me2 SiO2/2)0.895 (MePh SiO2/2)0.100
[0018] Furthermore, constituent (A-1) may be represented by organopolysiloxanes expressed by the average molecular formulas given below, Vi and Me are the same as defined above.
(MeVi SiO2/2)3
(MeVi SiO2/2)4
(MeViSiO2/2)5
[0019] Constituent (A-2) is an organopolysiloxane that is intended for imparting hardness and mechanical strength to a cured body of the composition. This constituent is represented by the following average compositional formula:
(R23 SiO1/2)e (R22 SiO2/2)f(R2 SiO3/2)g (SiO4/2)h (HO1/2)i
[0020] In this formula, R2 designates phenyl groups, methyl groups, or alkenyl groups having 2 to 10 carbon atoms. The alkenyl groups of R2 can be represented by vinyl, allyl, butenyl, pentenyl, or hexenyl groups. Vinyl groups are preferable in view of their reactivity and ease of synthesis. However, 5 to 10 mole % of all R2 groups are alkenyl groups. This is because if the content of the alkenyl groups is below the recommended lower limit, a cured body of the composition will have low hardness and mechanical strength, and if, on the other hand, the content of the alkenyl group exceeds the recommended upper limit, a cured body will become brittle. Furthermore, when the sum of methyl groups and phenyl groups of R2 is assumed as 100%, the methyl groups should constitute 90 mole % of more. This is because if the content of methyl groups is lower than the recommended limit, a cured body of the composition can easily acquire a color at a high temperature. Furthermore, in the above formula, "e", "f", "g", "h" and "i" are numbers that represent ratios of siloxane structural units and hydroxyl groups, and that satisfy the following conditions: 0.4 ≤ e ≤ 0.6; 0 ≤ f ≤ 0.05; 0 ≤ g ≤ 0.05; 0.4 ≤ h ≤ 0.6; 0.01 ≤ i ≤ 0.05; and e+f+g+h =1. If the value of "e" is below the recommended lower limit, this will reduce mechanical strength of a cured body, and if, on the other hand, the value of "e" exceeds the recommended upper limit, it will be impossible to impart to a cured body a sufficient hardness. If the value of "f" exceeds the recommended upper limit, it will be impossible to impart to a cured body a sufficient hardness. If the value of "g" exceeds the recommended upper limit, this will lower mechanical strength of a cured body. If the value of "h" is below the recommended lower limit, it will be impossible to impart to a cured body a sufficient hardness, and if, on the other hand, the value of "h" exceeds the recommended upper limit, it will impair dispersibility of the component in the composition and will reduce mechanical strength of a cured body of the composition. Finally, in order to provide the composition with good bondability, it is important to maintain the value of "i" within the recommended range. If the value of "i" is below the recommended lower limit, it will be impossible to provide the composition with desired bonding properties, and if, on the other hand, the value of "i" exceeds the recommended upper limit, this will impair dispersibility of this constituent in the composition and will not allow imparting desired mechanical strength and bonding properties to a cured body of the composition. Constituent (A-2) may have a branched or net-like molecular structure. There are no special restrictions with regard to viscosity of this constituent at 25°C and it may be liquid or solid provided that it is miscible with constituent (A-1).
[0021] Constituent (A-2) may be represented by organopolysiloxanes expressed by the average compositional formulas given below, where Vi, Me, and Ph are the same as defined above.
(ViMe2 SiO1/2)0.10 (Me3 SiO1/2)0.33 (SiO4/2)0.57 (HO1/2)0.03
(ViMe2 SiO1/2)0.13 (Me3 SiO1/2)0.35 (SiO4/2)0.52 (HO1/2)0.02
(ViMePh SiO1/2)0.10 (Me3 SiO1/2)0.33 (SiO4/2)0.57 (HO1/2)0.03
(ViMe2 SiO1/2)0.09 (Me3 SiO1/2)0.31 (SiO4/2)0.60 (HO1/2)0.04
(ViMe2 SiO1/2)0.10 (Me3 SiO1/2)0.40 (SiO4/2)0.50 (HO1/2)0.03
[0022] It is recommended that component (A) contains 40 to 70 wt.% of constituent (A-1) and 30 to 60 wt.% of constituent (A-2), and preferably 45 to 65 wt.% of constituent (A-1) and 35 to 55 wt.% of constituent (A-2). If the content of constituent (A-1) exceeds the recommended upper limit, it will be impossible to impart a desired hardness and mechanical strength to a cured body of the composition, and if, on the other hand, the content of constituent (A-1) is below the recommended lower limit, this will impair handleability of the composition and impart brittleness to a cured body.
[0023] It is not necessary to premix constituents (A-1) and (A-2) of component (A) if the composition can be eventually prepared in a state of high uniformity. From the viewpoint of good handleability, component (A) should be liquid at 25°C and have a viscosity in the range of 100 to 5,000,000 mPa·s, preferably 500 to 100,000 mPa·s.
[0024] Component (B) is used in the composition as a cross-linking agent. It comprises an organopolysiloxane that has silicon-bonded hydrogen atoms and consists of constituents (B-1), (B-2), and, if necessary, constituent (B-3).
[0025] Constituent (B-1) acts not only as a cross-linking agent but also as an efficient interfacial bonding improver. This constituent comprises an organopolysiloxane that is represented by the following average molecular formula:
R33 SiO (R32 SiO)j (R3H SiO)k SiR33
[0026] In this formula, R3 designates phenyl groups or methyl groups; methyl groups constitute 90 mole % or more of all groups contained in R3. If the content of methyl groups is below the recommended limit, a cured body will acquire a color at a high temperature. In this formula, "j" is a number in the range of 0 to 35; and "k" is a number in the range of 5 to 100. If the value of "j" exceeds the recommended upper limit, it will be impossible to provide the composition with good bondability. If the value of "k" is below the recommended lower limit, it will be impossible to provide the composition with good bondability, and if, on the other hand, the value of "k" exceeds the recommended upper limit, a cured body will be obtained with low mechanical strength. Furthermore, the content of silicon-bonded hydrogen atoms should be equal to or greater than 0.5 wt.%. If the content of silicon-bonded hydrogen atoms is below 0.5 wt.%, it will be difficult to provide the composition with good bondability. It is recommended that constituent (B-1) be liquid at 25°C and have viscosity at 25°C in the range of 3 to 10,000 mPa·s, preferably 5 to 5,000 mPa·s. If the viscosity is below the recommended lower limit, a cured body, this will impair mechanical strength and bonding strength, and if, on the other hand, the viscosity exceeds the recommended upper limit, this will impair handleability of the composition.
[0027] Constituent (B-1) may be represented by organopolysiloxanes expressed by the average molecular formulas given below, where Me and Ph are the same as defined above.
Me3 SiO (MeH SiO)10 SiMe3
Me3 SiO (MeH SiO)80 SiMe3
Me3 SiO (Me2 SiO)30(MeH SiO)30 SiMe3
PhMe2 SiO (MeH SiO)35 SiPhMe2
[0028] Constituent (B-2) acts not only as a cross-linking agent but also as an efficient agent for improving mechanical strength of a cured body as well as aggregation and bonding properties. Constituent (B-2) comprises an organopolysiloxane that is represented by the following average compositional formula:
(HR42 SiO1/2)l (R43 SiO1/2)m (R42 SiO2/2)n (R4 SiO3/2)o (SiO4/2)p (R5O1/2)q
[0029] In this formula, R4 designates phenyl groups or methyl groups. Methyl groups constitute 90 mole % or more of all groups contained in R4. If the content of methyl groups is below the recommended limit, this may color the cured body at a high temperature. In the above formula, R5 designates hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. The alkyl groups of R5 having 1 to 10 carbon atoms are represented by methyl, ethyl, and isopropyl groups. Furthermore, in the formula, "1", "m", "n", o", "p" and "q" are numbers that represent ratios of siloxane structural units and hydroxyl groups or alkoxy groups, and that satisfy the following conditions: 0.4 ≤ 1 ≤ 0.7; 0 ≤ m ≤ 0.2; 0 ≤ n ≤ 0.05; 0 ≤ or ≤ 0.5; 0.3 ≤ p ≤ 0.6; 0 ≤ q ≤ 0.05; and l+m+n+o+p = 1. If the value of "1" is below the recommended lower limit, it will be impossible to achieve a desired hardness, and if, on the other hand, the value of "1" exceeds the recommended upper limit, this will reduce molecular weight of the present constituent and will not allow imparting a sufficient mechanical strength to a cured body. Furthermore, if the value of "m" exceeds the recommended upper limit, it will be impossible to achieve a desired hardness. If the value of "n" exceeds the recommended upper limit, it will be impossible to achieve a desired hardness. If the value of "o" exceeds the recommended upper limit, this will impair dispersibility of the constituent and will not allow imparting a sufficient mechanical strength to a cured body. If the value of "p" is below the recommended lower limit, it will be impossible to achieve as a desired hardness, and if, on the other hand, the value of "p" exceeds the recommended upper limit, this will impair dispersibility of the present constituent in the composition and will not allow obtaining a desired mechanical strength. Finally, if the value of "q" exceeds the recommended upper limit, this will reduce molecular weight of the constituent and will not allow imparting a sufficient mechanical strength to a cured body. The present constituent should contain at least 0.5 wt.% of silicon-bonded hydrogen atoms. If the content of silicon-bonded hydrogen atoms is below 0.5 wt.%, it will be impossible to impart sufficient mechanical strength to a cured body. In order to improve miscibility of the present constituent with the composition, this constituent should be liquid or solid at 25°C.
[0030] Constituent (B-2) may be represented by organopolysiloxanes expressed by the average compositional formulas given below, where Me and Ph are the same as defined above.
(HMe2 SiO1/2)0.67 (SiO4/2)0.33
(HMe2 SiO1/2)0.50 (Me3 SiO1/2)0.17 (SiO4/2)0.33
(HMe2 SiO1/2)0.65 (Ph SiO3/2)0.05 (SiO4/2)0.30
[0031] Constituent (B-3) is an arbitrary component, which is used for controlling hardness of a cured body. This constituent is an organopolysiloxane represented by the following average molecular formula:
HR62 SiO (R62 SiO)r SiR62H
where R6 designates phenyl or methyl groups and where methyl groups constitute at least 90% of all groups contained in R6. If the content of methyl groups is below the recommended lower limit, this will color a cured body at a high temperature. In the above formula, "r" designates a number in the range of 10 to 100. If "r" is below the recommended lower limit, it will be difficult to provide a cured body with a desired hardness, and if, on the other hand, the value of "r" exceeds the recommended upper limit, a cured body will lose its mechanical strength.
[0032] Constituent (B-3) can be exemplified by organopolysiloxanes that are expressed by the following average molecular formulas, where Me and Ph are the same as defined above:
HMe2 SiO (Me2 SiO)20 SiMe2H
HMe2 SiO (Me2 SiO)80 SiMe2H
HMe2 SiO (Me2 SiO)50 (MePh SiO)5 SiMe2H
[0033] Component (B) contains 10 to 50 wt.% of constituent (B-1), 50 to 90 wt.% of constituent (B-2), and 0 to 30 wt.% of constituent (B-3), preferably 15 to 35 wt.% of constituent (B-1), 65 to 85 wt.% of constituent (B-2), and 0 to 25 wt.% of constituent (B-3). If the content of constituent (B-1) exceeds the recommended upper limit, this will reduce mechanical strength of a cured body, and if, on the other hand, the content of constituent (B-1) is below the recommended lower limit, this will reduce bonding properties of a cured body. If the content of constituent (B-2) exceeds the recommended upper limit, this will reduce bonding properties of a cured body, and if, on the other hand, the content of constituent (B-2) is below the recommended lower limit, this will reduce mechanical strength of a cured body. If the content of constituent (B-3) exceeds the recommended upper limit, this will reduce hardness of a cured body. It is not necessary to premix the aforementioned constituents of component (B) if it is eventually possible of obtained the final composition in a state of high uniformity. Component (B) is liuid at 25°C. From the viewpoint of good handleability, component (B) should be liquid at 25°C and have a viscosity in the range of 5 to 100,000 mPa·s, preferably 10 to 50,000 mPa·s.
[0034] Component (B) is added in such an amount that the silicon-bonded hydrogen atoms are in the range of 0.5 to 2.0 moles, preferably 0.8 to 1.8 moles, per 1 mole of the total content of alkenyl groups in component (A). If the content of component (B) is below the recommended lower limit, or exceeds the recommended upper limit, it will be impossible to impart to a cured body of the composition the desired hardness, mechanical characteristics, and bonding properties.
[0035] Component (C) is a hydrosilylation-reaction catalyst that is used for accelerating hydrosilylation reaction of the composition. Such a catalyst can be exemplified by a platinum-based catalyst, platinum-based compound catalyst, metallic platinum catalyst, rhodium-based catalyst, or a palladium-based catalyst. From the viewpoint of efficient acceleration of the hydrosilylation reaction of components (A) and (B) and thus for accelerated curing of the composition, it is recommended to employ a platinum-based catalyst. Such a catalyst can be represented by fine platinum powder, platinum black, chloroplatinic acid, an alcohol-modified chloroplatinic acid, a diolefin complex of chloroplatinic acid, an olefin complex of platinum; platinum bis(acetoacetate), platinum bis(acetoacetonate), or a similar platinum-carbonyl complex; a complex of chloroplatinic acid and divinyl-tetramethyl disiloxane, a complex of chloroplatinic acid and tetravinyl-tetramethyl-cyclotetrasilane, or a similar complex of chloroplatinic acid and alkenylsiloxane; a complex of platinum and divinyltetramethyl-disiloxane, a complex of platinum and tetravinyltetramethyl-cyclotetrasiloxane, or a similar complex of platinum and alkenylsiloxane; a complex of chloroplatinic acid and acetylene alcohol, etc. From the viewpoint of hydrosilylation efficiency, it is recommended to use a complex of platinum and an alkenylsiloxane.
[0036] The alkenylsiloxane may be exemplified by the following compounds: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane; 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetrasiloxane; alkenylsiloxane wherein a part of its methyl groups is substituted with ethyl groups, phenyl groups, etc.; or a similar substituted alkenylsiloxane oligomer; or an alkenylsiloxane oligomer wherein vinyl groups of its alkenylsiloxane are substituted with allyl, hexenyl, or similar groups. Due to the high stability of platinum-alkenylsiloxane complexes, it is recommended to use 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.
[0037] Furthermore, in order to further improve the stability of platinum-alkenylsiloxane complexes, they can be combined with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, or similar alkenylsiloxane oligomers or organosiloxane oligomers such as dimethylsiloxane oligomers, especially alkenylsiloxane oligomers.
[0038] There are no special restriction with regard to the amount in which component (C) can be used, provided that it accelerates curing of the composition. More specifically, it is recommended to add component (C) in such an amount that in terms of weight units the content of platinum-type metal atoms, in particular platinum atoms of this component is in the range of 0.01 to 500 ppm, preferably 0.01 to 100 ppm, and more preferably 0.1 to 50 ppm. If the content of component (C) is below the recommended lower limit, it will be difficult to provide sufficient curing, and if, on the other hand, the content of component (C) exceeds the recommended upper limit, this will lead to coloration of the cured body.
[0039] In order to improve handleability and bonding properties of the composition, it may be further provided with (D) fumed silica having BET specific area in the range of 20 to 200 m2/g. This component should be used in an amount of 1 to 10 parts by weight per 100 parts by weight of the sum of components (A), (B), and (C). If component (D) is used in such an amount that the BET specific area thereof is below or above the recommended range, this will impair handleability and will not allow obtaining a desired viscosity of the composition. Furthermore, if the content of component (D) exceeds the recommended upper limit, this will impair light transmitting properties.
[0040] In order to extend the pot life and storage stability at room temperature, the composition can be further provided with component (E) such as 1-ethynylcyclohexan-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, or similar alkyne alcohols; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, or similar ene-yne compounds; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, or similar methylalkenylsiloxane oligomers; dimethyl bis(3-methyl-1-butyn-3-oxy)silane, methylvinyl bis(3-methyl-1-butyn-3-oxy)silane, or similar alkynoxysilanes; benzotriazole, or similar hydrosilylation reaction inhibitors.
[0041] Component (E) is used in an amount sufficient for inhibiting gelling or curing the composition during mixing of components (A), (B), and (C) and also in an amount needed for providing long-term storage of the composition. More specifically, it is recommended to add this component in an amount of 0.0001 to 5 parts by weight, preferably 0.01 to 3 parts by weight per 100 parts by weight of the sum of components (A), (B), and (C).
[0042] Moreover, to further improve bonding to the substrate that is in contact with the composition during curing, the composition may be combined with (F) an adhesion promoter. Such an adhesion promoter may be one known in the art and used for addition to hydrosilylation-reaction curable organopolysiloxane compositions.
[0043] Component (F) may be exemplified by the following compounds: organosilanes or organosiloxane oligomers having 4 to 20 silicon atoms and a linear, branched, or cyclic molecular structure and containing trialkoxysiloxy groups (such as trimethoxysiloxy groups or triethoxysiloxy groups) or trialkoxysilylalkyl groups (such as trimethoxysilylethyl groups or triethoxysilylethyl groups) and hydrosilyl groups or alkenyl groups (such as vinyl groups or allyl groups); organosilanes or organosiloxane oligomers having 4 to 20 silicon atoms and a linear, branched, or cyclic molecular structure and containing trialkoxysiloxy groups or trialkoxysilylalkyl groups and methacryloxyalkyl groups (such as 3-methacryloxypropyl groups); organosilanes or organosiloxane oligomers having 4 to 20 silicon atoms and a linear, branched, or cyclic molecular structure and containing trialkoxysiloxy groups or trialkoxysilylalkyl groups and epoxy-containing alkyl groups (such as 3-glycidoxypropyl groups, 4-glycidoxybutyl groups, 2-(3,4-epoxycyclohexyl)ethyl groups, or 3-(3,4-epoxycyclohexyl)propyl groups); reaction products of aminoalkyltrialkoxysilane and epoxy-bonded alkyltrialkoxysilane; or epoxy-containing ethylpolysilicate. Specific examples are the following compounds: vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hydrogentriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, reaction products of 3-glycidoxypropyltriethoxysilane and 3-aminopropyltriethoxysilane; condensation reaction products of 3-glycidoxypropyltrimethoxysilane and methylvinylsiloxane oligomer capped with silanol groups; condensation reaction products of 3-methacryloxypropyltriethoxysilane and methylvinylsiloxane oligomer capped with silanol groups; and tris(3-trimethoxysilylpropyl)isocyanurate.
[0044] From the viewpoint of preventing a decrease in resistance to yellowing and in light transparency, when a cured body is used over a long time at elevated temperatures, it is preferable that component (F) does not contain active nitrogen atoms, e.g., amino groups. This adhesion promoter is preferably a low-viscosity liquid that has a viscosity at 25°C in the range of 1 to 500 mPa·s.
[0045] Component (F) should be added in amounts that do not impair curing properties, in particular do not cause change of color in a cured body. More specifically, it should be added in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the sum of components (A), (B), and (C).
[0046] Within the limits not contradicting with the object of the invention, besides component (D), the composition may contain other arbitrary components such as silica, glass, zinc oxide or similar inorganic fillers; silicone rubber powder; silicone resin, polymethacrylate resin, or similar resin powders; heat-resistant agents, dyes, pigments, flame retarders, solvents, etc.
[0047] From the viewpoint of handling, it is recommended that the composition is liquid and have a viscosity at 25°C in the range of 10 to 1,000,000 mPa·s. If the composition is intended for use as a sealant for optical semiconductor elements, it should have a viscosity at 25°C in the range of 100 to 10,000 mPa·s, and if it is intended for use as a bonding agent for optical semiconductor elements, it should have a viscosity at 25°C in the range of 1,000 to 500,000 mPa·s.
[0048] The composition is cured by retaining at room temperature or by heating. For acceleration of curing, it is recommended to cure the composition by heating. The heating temperature should be in the range of 50 to 200°C.
[0049] The composition provides excellent bonding durability, with respect to steel, stainless steel, aluminum, copper, silver, titanium, titanium alloy or other metals or alloys; silicon semiconductors, gallium-phosphorus-based semiconductors, gallium-arsenide-based semiconductors, gallium-nitride-based semiconductors, or similar semiconductor elements; ceramics, glass, thermosetting resins, and thermoplastic resins that contain polar groups, and in particular if the above objects are subject to heating-cooling cycles.
[0050] It is recommended that curing of the composition produce a cured body having hardness measured by type A durometer in accordance with JIS K 6253 in the range of 70 to 90. If the cured body has the hardness below the recommended lower limit, it will have poor cohesion and insufficient strength and bonding capacity, and if, on the other hand, the hardness exceed the recommended upper limit, a cured body will acquire brittleness, and it will be impossible to provide sufficient bonding properties.
[0052] The optical semiconductor device of the invention comprises an optical semiconductor element that is either sealed in a housing by a cured body of a sealing material formed from the composition of the present invention, or is bonded to the housing with a cured body of a bonding material formed from the composition of the invention. The optical semiconductor element may comprise a light-emitting diode (LED), semiconductor laser, photodiode, photo transistor, solid-state image pickup elements, or a photo-coupler light emitter and receiver. Most suitable application is a LED.
[0053] Since in a LED the light is emitted from the semiconductor in a vertical and in a horizontal direction, it is required that the parts of the device be made from materials that do not absorb the light and have either high light transmittance or high coefficient of light reflection. A substrate that supports the optical semiconductor element is also not an exception from this rule. Such a substrate can be made from silver, gold, copper, or another electrically conductive metal; aluminum, nickel or another non-electroconductive metal; PPA (Polyphthalamide), LCP (Liquid Crystal Polymer), or another thermoplastic resin mixed with a white pigment; epoxy resin, BT resin, polyimide resin, silicone resin, or a similar thermosetting resin mixed with a white pigment; alumina, alumina nitride, or similar ceramics. Since the composition of the invention provides good bonding to semiconductor elements and substrates, it improves reliability of the obtained optical semiconductor device.
[0054] The optical semiconductor device of the invention is described in more detail with reference to Fig. 1. Fig. 1 is a sectional view of a single surface-mount type LED shown as a typical example of an optical semiconductor device. The LED of Fig. 1 comprises a LED chip 5 which is die-bonded to a die pad 3 through a bonding material 4 inside a housing 1 made from a polyphthalamide resin (PPA). The LED chip 5, in turn, is wire-bonded to inner leads 2 by bonding wires 6, and along with the inner walls of the housing are sealed with a sealing material 7. In the LED of the invention, the composition that is used for forming the bonding material 4 and/or the sealing material 7 is the curable organopolysiloxane composition of the present invention.
Examples
[0055] The curable organopolysiloxane composition of the present invention and the optical semiconductor device of the invention will be further illustrated in more details with reference to application and comparative examples. In these application and comparative examples, the values of viscosity corresponds to 25°C.
[0056] Listed below are formulas of the constituents that were used for the preparation of curable organopolysiloxane compositions shown in the application and comparative examples, wherein Vi stands for vinyl groups, Me stands for methyl groups, and Ph stands for phenyl groups; Vi% shows the percentage of vinyl groups (mole %) in all organic groups, and Me% shows the percentage of methyl groups (mole %) in the sum of methyl groups and phenyl groups. Furthermore, in the tables, the SiH/Vi ratio is the ratio of the total number of silicon-bonded hydrogen atoms in constituents (b-1) to (b-6) to 1 mole of the sum of vinyl groups in constituents (a-1) to (a-9) contained in the composition.
| Constituent (a-1): | organopolysiloxane (Vi% = 2.06 mole %; Me% = 100 mole %) having viscosity of 60 mPa·s and represented by the following average compositional formula: |
| (Me2Vi SiO1/2)0.042 (Me2 SiO2/2)0.958 | |
| Constituent (a-2): | organopolysiloxane (Vi% = 0.60 mole %; Me% = 100 mole %) having viscosity of 550 mPa·s and represented by the following average compositional formula: |
| (Me2Vi SiO1/2)0.012 (Me2Si2/2)0.988 | |
| Constituent (a-3): | organopolysiloxane (Vi% = 50 mole %; Me% = 100 mole %) having viscosity of 4 mPa·s and represented by the following average molecular formula: |
| (MeVi SiO2/2)4 | |
| Constituent (a-4): | organopolysiloxane (Vi% = 5.8 mole %; Me% = 100 mole %) which is solid at 25°C and is represented by the following average compositional formula: |
| (Me2Vi SiO1/2)0.09 (Me3 SiO1/2)0.43 (SiO4/2)0.48 (HO1/2)0.03 | |
| Constituent (a-5): | organopolysiloxane (Vi% = 6.1 mole %; Me% = 100 mole %) which is solid at 25°C and is represented by the following average compositional formula: |
| (Me2Vi SiO1/2)0.10 (Me3 SiO1/2)0.45 (SiO4/2)0.45 (HO1/2)0.02 | |
| Constituent (a-6): | organopolysiloxane (Vi% = 5.8 mole %; Me% = 100 mole %) which is solid at 25°C and is represented by the following average compositional formula: |
| (Me2 Vi SiO1/2)0.09 (Me3 SiO1/2)0.43 (SiO4/)0.48 (H1/2)0.005 | |
| Constituent (a-7): | organopolysiloxane (Vi% = 6.4 mole %; Me% = 100 mole %) which is solid at 25°C and is represented by the following average compositional formula: |
| (Me2Vi SiO1/2)0.10 (Me3 SiO1/2)0.42 (SiO4/2)0.48 (HO1/2)0.07 | |
| Constituent (a-8): | organopolysiloxane (Vi% = 8.5 mole %; Me% = 100 mole %) which is solid at 25°C and is represented by the following average compositional formula: |
| (Me2Vi SiO1/2)0.17 (Me3 SiO1/2)0.50 (SiO4/2)0.33 (HO1/2)0.04 | |
| Constituent (a-9): | organopolysiloxane (Vi% = 4.8 mole %; Me% = 100 mole %) which has viscosity of 500 mPa·s at 25°C and is represented by the following average compositional formula: |
| (Me2Vi SiO1/2)0.05 (Me3 SiO1/2)0.30 (SiO4/2)0.65 (HO1//2)0.03 | |
| Constituent (b-1): | organopolysiloxane (Me% = 100 mole %) which has viscosity of 10 mPa·s, contains 1.3 wt.% of silicon-bonded hydrogen atoms, and is represented by the following average molecular formula: |
| Me3 SiO (MeH SiO)10 SiMe3 | |
| Constituent (b-2): | organopolysiloxane (Me% = 100 mole %) which has viscosity of 200 mPa·s, contains 0.72 wt.% of silicon-bonded hydrogen atoms, and is represented by the following average molecular formula: |
| Me3 SiO (Me2 SiO)30 (MeH SiO)30 SiMe3 | |
| Constituent (b-3): | organopolysiloxane (Me% = 100 mole %) which has viscosity of 200 mPa·s, contains 0.34 wt.% of silicon-bonded hydrogen atoms, and is represented by the following average molecular formula: |
| Me3 SiO (Me2 SiO)45 (MeH SiO)15 SiMe3 | |
| Constituent (b-4): | organopolysiloxane (Me% = 100 mole %) which has viscosity of 120 mPa·s, contains 1.03 wt.% of silicon-bonded hydrogen atoms, and is represented by the following average compositional formula: |
| (HMe2 SiO1/2)0.67 (SiO4/2)0.33 | |
| Constituent (b-5): | organopolysiloxane (Me% = 100 mole %) which has viscosity of 130 mPa·s, contains 0.74 wt.% of silicon-bonded hydrogen atoms, and is represented by the following average compositional formula: |
| (HMe2 SiO1/2)0.50 (Me3 SiO1/2)0.17 (SiO4/2)0.33 | |
| Constituent (b-6): | organopolysiloxane (Me% = 75 mole %) which has viscosity of 200 mPa·s, contains 0.65 wt.% of silicon-bonded hydrogen atoms, and is represented by the following average compositional formula: |
| (HMe2 SiO1/2)0.60 (PhSiO3/2)0.40 | |
| Constituent (c): | 1.3-divinyl-1,1,3,3-tetramethyldisiloxane solution of complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (contains about 4 wt.% of metallic platinum) |
| Constituent (d-1): | fumed silica having BET surface area in the range of 115 to 165 m2/g and hydrophobized by surface treatment with hexamethyl disilazane (RX200, the product of Nippon Aerosil Co., Ltd.) |
| Constituent (d-2): | fumed silica having BET surface area in the range of 30 to 50 m2/g and hydrophobized by surface treatment with hexamethyl disilazane (NAX50, the product of Nippon Aerosil Co., Ltd.) |
| Constituent (e): | 1-ethynylcyclohexan-1-ol |
| Constituent (f): | condensation reaction product of 3-glycidoxypropyltrimethoxysilane and methylvinylsiloxane oligomer capped at both molecular terminals with silanol groups and having viscosity of 30 mPa·s. |
[0057] Viscosity of the curable organopolysiloxane compositions, as well as hardness, light transmittance, and bonding strength of the cured bodies mentioned in the application and comparative examples were measured by the methods described below.
[Viscosity of the Curable Organopolysiloxane Composition]
[0058] This characteristic was measured after the preparation of the curable organopolysiloxane composition within 30 min. by means of a viscometer (AR-550, the product of TA Instrument Co., Ltd.) and by using a 2° cone plate of 20 mm diameter at a shear speed of 10 (1/s).
[Hardness of Cured Body]
[0059] The curable organopolysiloxane was formed into a cured sheet-like body by press forming for 1 hour at 150°C, and the latter was used for measuring hardness with type A durometer according to JIS K 6253.
[0060] Furthermore, the sheet-like cured body was retained for 1,000 hours in an oven at 150°C, and then hardness after heat-resistance test was measured by the same method as mentioned above.
[Light-Transmitting Properties of Cured Body]
[0061] The curable organopolysiloxane composition was sandwiched between two glass plates and cured by holding it for 1 hour at 150°C. Light-transmitting properties of the obtained cured body were measured at 25°C by a self-recording spectrophotometer (optical path: 0.1 cm) capable of measuring at any wavelength of visible light (the wavelength range of 400 nm to 700 nm). Light transmission through the cured body was determined by subtracting light transmission through the glass only from light transmission through the glass and the composition. The light transmittance obtained for wavelength 450 nm is shown in Table 1.
[0062] Furthermore, the aforementioned cured body was retained for 1,000 hours in an oven at 150°C, and then light transmittance after heat-resistance test was measured by the same method as mentioned above.
[Bonding Strength of Cured Body]
[0063] Spacers made from polytetrafluoroethylene (width: 10 mm; length:20 mm; thickness: 1 mm) were sandwiched between two silver-plated steel plates (width: 25 mm; length: 50 mm; thickness: 1 mm). The gap between the plates was filled with the curable organopolysiloxane composition, the plates were clipped together, and the composition was cured by retaining the unit for 1 hour at 150°C in a hot-air-circulation type oven. After cooling to room temperature, the clip and the spacers were removed, and the bonding strength of a cured body was measured by stretching the obtained specimen in mutually opposite horizontal directions in a tensile test machine.
[0064] Furthermore, the aforementioned specimen was retained for 1000 hours in an oven at 150°C, and then the bonding strength after heat-resistance test was measured by the same method as mentioned above.
[Application Examples 1 to 4, Comparative Examples 1 to 6]
[0065] Curable organopolysiloxane compositions were prepared with component ratios shown in Table 1. Properties of cured bodies measured as described above are also shown in Table 1.
[Application Examples 5 to 8, Comparative Examples 7 to 12]
[0066] Curable organopolysiloxane compositions were prepared with component ratios shown in Table 2. Properties of cured bodies measured as described above are also shown in Table 2.
Industrial Applicability
[0067] The curable organopolysiloxane composition of the invention can be used as a sealant and a bonding agent for optical semiconductor elements of LEDs, semiconductor lasers, photodiodes, photo transistors, solid-state image pickup elements, photo-coupler light emitters and receivers, etc. The optical semiconductor devices of the invention may be used as optical devices, optical instruments, lighting devices, illumination devices, or similar optical semiconductor devices.
(A) an alkenyl-containing organopolysiloxane that comprises 40 to 70 wt.% of constituent
(A-1) and 30 to 60 wt.% of constituent (A-2), wherein
constituent (A-1) comprises an organopolysiloxane of the following average compositional
formula:
(R13 SiO1/2)a (R12 SiO2/2)b (R1 SiO3/2)c (SiO4/2)d
where R1 designates phenyl groups, methyl groups, or alkenyl groups having 2 to 10 carbon
atoms; 0.1 to 50 mole % of all R1 groups are alkenyl groups having 2 to 10 carbon atoms; methyl groups constitute 90
mole % or more of the sum of methyl and phenyl groups contained in R1; "a", "b", "c", and "d" are numbers that satisfy the following conditions: 0 ≤ a
≤ 0.05; 0.9 ≤ b ≤ 1; 0 ≤ c ≤ 0.03; 0 ≤ d ≤ 0.03; and a+b+c+d = 1;
constituent (A-2) comprises an organopolysiloxane of the following average compositional
formula:
(R23 SiO1/2)e (R22 SiO2/2)f (R2 SiO3/2)g (SiO4/2)h (HO1/2)i
where R2 designates phenyl groups, methyl groups, or alkenyl groups having 2 to 10 carbon
atoms; 5 to 10 mole % of all R2 groups are alkenyl groups having 2 to 10 carbon atoms; methyl groups constitute 90
mole % or more of the sum of methyl and phenyl groups contained in R2; "e", "f", "g", "h" and "i" are numbers that satisfy the following conditions: 0.4
≤ e ≤ 0.6; 0 ≤ f ≤ 0.05; 0 ≤ g ≤ 0.05; 0.4 ≤ h ≤ 0.6; 0.01 ≤ i ≤ 0.05; and e+f+g+h
= 1;
(B) an organopolysiloxane that contains silicon-bonded hydrogen atom and comprises
10 to 50 wt.% of constituent (B-1), 50 to 90 wt.% of constituent (B-2), and 0 to 30
wt.% of constituent (B-3); in an amount that the silicon-bonded hydrogen atoms in
component (B) are in the range of 0.5 to 2.0 moles per 1 mole of the total content
of alkenyl groups in component (A), wherein
constituent (B-1) comprises an organopolysiloxane that contains at least 0.5 wt.%
of silicon-bonded hydrogen atoms and that is represented by the following average
molecular formula:
R33 SiO (R32 SiO)j (R3H SiO)k SiR33
where R3 designates phenyl groups or methyl groups; methyl groups constitute 90 mole % or
more of all groups contained in R3; "j" is a number in the range of 0 to 35; and "k" is a number in the range of 5 to
100;
constituent (B-2) comprises an organopolysiloxane that contains at least 0.5 wt.%
of silicon-bonded hydrogen atoms and that is represented by the following average
compositional formula:
(HR42 SiO1/2)l (R43 SiO1/2)m (R42 SiO2/2)n (R4 SiO3/2)o (SiO4/2)p (R5O1/2)q
where R4 designates phenyl groups or methyl groups; methyl groups constitute 90 mole % or
more of all groups contained in R4; R5 designates hydrogen atoms or alkyl groups having 1 to 10 carbon atoms; and "l", "m",
"n", "o", "p" and "q" are numbers that satisfy the following conditions: 0.4 ≤ l ≤
0.7; 0 ≤ m ≤ 0.2; 0 ≤ n ≤ 0.05; 0 ≤ o ≤ 0.5; 0.3 ≤ p ≤ 0.6; 0 ≤ q ≤ 0.05; and l+m+n+o+p
= 1;
constituent (B-3) is an organopolysiloxane represented by the following average molecular
formula:
HR62 SiO (R62 SiO)r SiR62H
where R6 represents phenyl or methyl groups; methyl groups constitute at least 90% of all
groups contained in R6; and "r" is a number in the range of 10 to 100; and
(C) a hydrosilylation-reaction catalyst, in an amount sufficient for curing the composition.
(A) ein alkenylhaltiges Organopolysiloxan, das zu 40 bis 70 Gew.-% Bestandteil (A-1)
und zu 30 bis 60 Gew.-% Bestandteil (A-2) umfasst, wobei
Bestandteil (A-1) ein Organopolysiloxan der folgenden durchschnittlichen Zusammensetzungsformel
umfasst:
(R13SiO1/2)a (R12SiO2/2)b (R1SiO3/2)c(SiO4/2)d
wobei R1 Phenylgruppen, Methylgruppen oder Alkenylgruppen mit 2 bis 10 Kohlenstoffatomen bezeichnet,
0,1 bis 50 Mol-% aller R1-Gruppen Alkenylgruppen mit 2 bis 10 Kohlenstoffatomen sind, Methylgruppen 90 Mol-%
oder mehr der der in R1 enthaltenen Summe von Methyl- und Phenylgruppen ausmachen, "a", "b", "c" und "d"
Zahlen sind, die die folgenden Bedingungen erfüllen: 0 ≤ a ≤ 0,05, 0,9 ≤ b ≤ 1, 0
≤ c ≤ 0,03, 0 ≤ d ≤ 0,03, und a+b+c+d = 1,
Bestandteil (A-2) ein Organopolysiloxan der folgenden durchschnittlichen Zusammensetzungsformel
umfasst:
(R23SiO1/2)e (R22 SiO2/2)f(R2 SiO3/2)g (SiO4/2)h (HO1/2)i
wobei R2 Phenylgruppen, Methylgruppen oder Alkenylgruppen mit 2 bis 10 Kohlenstoffatomen bezeichnet,
5 bis 10 Mol % aller R2-Gruppen Alkenylgruppen mit 2 bis 10 Kohlenstoffatomen sind, Methylgruppen 90 Mol-%
oder mehr der der in R2 enthaltenen Summe aus Methyl- und Phenylgruppen bilden, "e", "f", "g" und "h" Zahlen
sind, die die folgenden Bedingungen erfüllen: 0,4 ≤ e ≤ 0,6, 0 ≤ f ≤ 0,05, 0 ≤ g ≤
0,05, 0,4 ≤ h ≤ 0,6, 0,01 ≤ i ≤ 0,05, und e+f+g+h =1,
(B) ein Organopolysiloxan, das siliciumgebundene Wasserstoffatome enthält und zu 10
bis 50 Gew.-% Bestandteil (B-1), zu 50 bis 90 Gew.-% Bestandteil (B-2) und zu 0 bis
30 Gew.-% Bestandteil (B-3) umfasst, in einer solchen Menge, dass die siliciumgebundenen
Wasserstoffatome im Bestandteil (B) im Bereich von 0,5 bis 2,0 Mol pro 1 Mol des Gesamtgehalts
an Alkenylgruppen im Bestandteil (A) vorliegen, wobei
Bestandteil (B-1) ein Organopolysiloxan umfasst, das zu mindestens 0,5 Gew.-% siliciumgebundene
Wasserstoffatome enthält und durch die folgende durchschnittliche Molekularformel
dargestellt wird:
R33 SiO (R32 SiO)j (R3H SiO)k SiR33
wobei R3 Phenylgruppen oder Methylgruppen bezeichnet, Methylgruppen 90 Mol.% oder mehr aller
der in R3 enthaltenen Gruppen ausmachen, "j" eine Zahl im Bereich von 0 bis 35 ist, und "k"
eine Zahl im Bereich von 5 bis 100 ist,
Bestandteil (B-2) ein Organopolysiloxan umfasst, das zu mindestens 0,5 Gew.-% siliciumgebundene
Wasserstoffatome enthält und das durch die folgende durchschnittliche Zusammensetzungsformel
dargestellt wird:
(HR42SiO1/2)l(R43SiO1/2)m (R42 SiO2/2)n (R4 SiO3/2)o (SiO4/2)p (R5O1/2)q
wobei R4 Phenylgruppen oder Methylgruppen bezeichnet, Methylgruppen 90 Mol.% oder mehr aller
der in R4 enthaltenen Gruppen ausmachen, R5 Wasserstoffatome oder Alkylgruppen mit 1 bis 10 Kohlenstoffatomen bezeichnet, und
"l", "m", "n", "o", "p" und "q" Zahlen sind, die die folgenden Bedingungen erfüllen:
0,4 ≤ 1 ≤ 0,7, 0 ≤ m ≤ 0,2, 0 ≤ n ≤ 0,05, 0 ≤ o ≤ 0,5, 0,3 ≤ p ≤ 0,6, 0 ≤ q ≤ 0,05,
und l+m+n+o+p = 1,
Bestandteil (B-3) ein Organopolysiloxan ist, das durch die folgende durchschnittliche
Molekularlformel dargestellt wird,
HR62SiO (R62 SiO)r SiR62H
wobei R6 für Phenyl- oder Methylgruppen steht, Methylgruppen mindestens 90 Mol.% aller der
in R6 enthaltenen Gruppen ausmachen, und "r" eine Zahl im Bereich von 10 bis 100 ist, und
(C) einen Katalysator für eine Hydrosilylierungsreaktion in einer zur Aushärtung der Zusammensetzung ausreichenden Menge.
(A) un organopolysiloxane contenant un alcényle qui comprend 40 à 70 % en poids de
constituant (A-1) et 30 à 60 % en poids de constituant (A-2), dans laquelle
le constituant (A-1) comprend un organopolysiloxane ayant la formule de composition
moyenne suivante :
(R13SiO1/2)a (R12SiO2/2)b (R1SiO3/2)c(SiO4/2)d
où R1 désigne des groupes phényle, des groupes méthyle, ou des groupes alcényle ayant 2
à 10 atomes de carbone ; 0,1 à 50 % molaires de tous les groupes R1 sont des groupes alcényle ayant 2 à 10 atomes de carbone ; les groupes méthyle représentent
90 % molaires ou plus de la somme des groupes méthyle et phényle contenus dans R1 ; « a », « b », « c », et « d » sont des nombres qui satisfont les conditions suivantes
: 0 ≤ a ≤ 0,05 ; 0,9 ≤ b ≤ 1 ; 0 ≤ c ≤ 0,03 ; 0 ≤ d ≤ 0,03 ; et a+b+c+d = 1 ;
le constituant (A-2) comprend un organopolysiloxane ayant la formule de composition
moyenne suivante :
(R23 SiO1/2)e (R22 SiO2/2)f(R2 SiO3/2)g (SiO4/2)h (HO1/2)i
où R2 désigne des groupes phényle, des groupes méthyle, ou des groupes alcényle ayant 2
à 10 atomes de carbone ; 5 à 10 % molaires de tous les groupes R2 sont des groupes alcényle ayant 2 à 10 atomes de carbone ; les groupes méthyle représentent
90 % molaires ou plus de la somme des groupes méthyle et phényle contenus dans R2 ; « e », « f », « g », « h » et « i » sont des nombres qui satisfont les conditions
suivantes : 0,4 ≤ e ≤ 0,6; 0 ≤ f ≤ 0,05 ; 0 ≤ g ≤ 0,05 ; 0,4 ≤ h ≤ 0,6 ; 0,01 ≤ i
0,05 ; et e+f+g+h=l ;
(B) un organopolysiloxane qui contient un atome d'hydrogène lié au silicium et comprend
10 à 50 % en poids de constituant (B-1), 50 à 90 % en poids de constituant (B-2),
et 0 à 30 % en poids de constituant (B-3) ; en une quantité telle que les atomes d'hydrogène
liés au silicium dans le composant (B) sont dans l'intervalle de 0,5 à 2,0 moles pour
1 mole de la teneur totale en groupes alcényle dans le composant (A), dans laquelle
le constituant (B-1) comprend un organopolysiloxane qui contient au moins 0,5 % en
poids d'atomes d'hydrogène liés au silicium et qui est représenté par la formule moléculaire
moyenne suivante :
R33 SiO (R32 SiO)j (R3H SiO)k SiR33
où R3 désigne des groupes phényle ou des groupes méthyle ; les groupes méthyle représentent
90 % molaires ou plus de tous les groupes contenus dans R3 ; « j » est un nombre dans l'intervalle de 0 à 35 ; et « k » est un nombre dans l'intervalle
de 5 à 100 ;
le constituant (B-2) comprend un organopolysiloxane qui contient au moins 0,5 % en
poids d'atomes d'hydrogène liés au silicium et qui est représenté par la formule de
composition moyenne suivante :
(HR42SiO1/2)l(R43SiOl/2). (R42 SiO2/2)n (R4 SiO3/2)o (SiO4/2)p (R5O1/2)q
où R4 désigne des groupes phényle ou des groupes méthyle ; les groupes méthyle représentent
90 % molaires ou plus de tous les groupes contenus dans R4 ; R5 désigne des atomes d'hydrogène ou des groupes alkyle comportant 1 à 10 atomes de
carbone ; et « 1 », « m », « n », « o », « p » et « q » sont des nombres qui satisfont
les conditions suivantes : 0,4 ≤ 1 ≤ 0,7 ; 0 ≤ m ≤ 0,2 ; 0 ≤ n ≤ 0,05 ; 0 ≤ o ≤ 0,5
; 0,3 ≤ p ≤ 0,6 ; 0 ≤ q ≤ 0,05 ; et l+m+n+o+p = 1 ;
le constituant (B-3) est un organopolysiloxane représenté par la formule moléculaire
moyenne suivante :
HR62SiO (R62 SiO)r SiR62H
où R6 représente des groupes phényle ou méthyle ; les groupes méthyle représentent au moins
90 % de tous les groupes contenus dans R6 ; et « r » est un nombre dans l'intervalle de 10 à 100 ; et
(C) un catalyseur de réaction d'hydrosilylation, dans une quantité suffisante pour durcir la composition.
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.
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